磺酰脲类除草剂在土壤中的物理化学行为

本文就磺酰脲类除草剂在土壤中的行为与土壤有关因素间的关系进行了阐述。该类除草剂进入土壤过后，主要经受迁移、转化、吸附、降解等过程，而这些过程又受土壤ｐＨ、温度、湿度、微生物和有机质含量的影响。     

同位素示踪法在磺酰脲类除草剂残留分析中的应用

除草剂的同位素残留分析技术日益受到人们的重视,并取得了长足的发展。本文综述了利用同位素示踪技术对4种磺酰脲类除草剂的残留分析进展。     

重金属、磺酰脲类除草剂的植物基因应答及其交互作用

土壤污染日益成为威胁人类生存的重要问题,而且正呈现出多元化和复杂化的特点。土壤的重金属污染已被重点研究,大量与金属阳离子吸收、分布和解毒相关的通道蛋白、螯合剂以及伴侣蛋白的编码基因被发现和克隆;而土壤的农药污染,特别是磺酰脲类除草剂类污染研究却还主要集中在生理生化水平上。同时,两者复合污染研究更是鲜有报道,总体还处于探索阶段。本文重点将对现阶段重金属与磺酰脲类除草剂单因素的植物基因应答及其复合污染交互作用的研究进展,在基因类型和作用等方面分别进行综合性分析与阐述,并结合环境污染现状和国际研究前沿提出了今后研究的主要方向。     

基质固相分散萃取-高效液相色谱串联质谱法测定土壤中残留的磺酰脲类除草剂

建立了基质固相分散萃取-高效液相色谱串联质谱法(MSPD-HPLC-MS/MS)测定土壤中3种磺酰脲类除草剂(氯磺隆、甲磺隆、苯磺隆)残留的分析方法。对基于球磨的基质固相分散萃取条件进行了详细优化,最终确定最佳条件为:0.2 g土壤样品、0.8 g HC-C18粉末状分散剂与直径为8 mm的小钢珠一起球磨10 min后,转移至空的玻璃萃取小柱,用10 m L乙腈洗脱,氮气吹干后用甲醇定容至0.6 m L,再经0.22μm的滤膜抽滤后装入自动进样瓶中。用Syncronis C18反相色谱柱分离,以甲醇(A)~1‰甲酸溶液(B)为流动相进行梯度洗脱,选择反应监测(SRM)模式下进行检测。氯磺隆在20~200μg·kg~(-1),甲磺隆和苯磺隆在10~200μg·kg~(-1)范围内线性良好,相关系数r在0.997 9~0.999 5。土壤样品的平均加标回收率在84.7%~104.6%,相对标准偏差在4.5%~7.9%(n=5)。方法的检出限(S/N=3)0.32~0.68μg·kg~(-1)。该方法简单、效率高、干扰少、回收率高,满足土壤中除草剂的残留分析要求。     

一株高效氯嘧磺隆降解菌的分离鉴定及其降解机理初探

消除农业生产中除草剂残留是现代农业绿色发展的关键,为发掘更多磺酰脲类除草剂高效降解微生物资源,系统阐述氯嘧磺隆的微生物降解途径。以氯嘧磺隆为唯一氮源,从某磺酰脲类除草剂生产厂废水处理活性污泥中分离出的高效氯嘧磺隆降解菌LAM2021。生理生化特性和16S rRNA基因序列比对分析结果表明,该菌株属小坂菌属(Kosakonia sp.)。单因素试验结果经RSM优化后,菌株LAM2021在无机盐培养基中对50 mg/L氯嘧磺隆的最佳降解条件为:接种量5%、培养温度30℃、pH 6.0,11 h后降解率可达94.6%。利用高效液相色谱(HPLC)对接菌后降解体系内代谢产生的酸类物质进行分离与鉴定,结果表明产物主要为柠檬酸。推测菌株LAM2021受高浓度氯嘧磺隆胁迫,利用葡萄糖产生柠檬酸,通过降低环境pH使氯嘧磺隆发生水解,从而解除其胁迫。从菌株全基因组信息中发现有参与氯嘧磺隆降解的酯酶编码基因。采用液相色谱-质谱联用(LC-MS)对菌株LAM2021与氯嘧磺隆混合培养后的代谢产物进行检测与鉴定,共有5种主要物质被检测到。根据氯嘧磺隆的化学结构式和中间代谢产物特征,推测菌株LAM2021降解氯嘧磺隆的代谢途径为:氯嘧磺隆中的脲桥先水解断裂成2-氨基-4-氯-6-甲基嘧啶和邻甲酸乙酯苯磺酰胺,随后酯键被脱酯断裂成邻甲酸乙酯苯磺酰胺,最后环化为N-醛基糖精。     

除草剂降解真菌对氯嘧磺隆的降解作用

利用自行筛选和保存的3种高效降解真菌菌株,对氯嘧磺隆除草剂降解作用的影响进行了系统的研究,采用高效液相色谱法测定其降解率。真菌黑曲霉、黄曲霉、F8酿酒酵母均可以很好的降解氯嘧磺隆,其中黑曲霉的降解率最高,为96.52%;其次是黄曲霉为88.21%。混合菌株对氯嘧磺隆的降解效率均高于其单一菌株,真菌黑曲霉与黄曲霉混合菌株降解率最高,为98.74%;其次是真菌黑曲霉与F8混合菌株为98.22%。在培养基中随着氯嘧磺隆降解率的增加,反应液的pH逐渐降低。     

新一代除草剂在推进环境质量中的作用

新一代除草剂具有用药量少、除草活性高、选择性强、对哺乳动物低毒(对人的毒性甚至低于日常生活中的食盐)、在环境中易降解、在非靶标有机体内无积累作用等优良特性。这些特性正有效地改善当今的环境质量。80年代初发展起来的磺酰脲类除草剂是最具代表性的品种。本文介绍该类除草剂在国内外的发展简况,它们的优良特性在改善农业生态环境质量中的作用,以及在我国应用的意义。     

土壤中结合残留态甲磺隆的微生物降解研究

主要进行了优选菌株青霉 (Penicilliumsp .)对土壤中结合残留态甲磺隆的降解研究 ,结果表明 ,优选菌株的引入对土壤中可提态甲磺隆的影响不大 ,但对结合残留态甲磺隆的降解和矿化有较大影响。在结合残留态甲磺隆中 ,优选菌株青霉的引入有利于松结态甲磺隆尤其是松结态富里酸甲磺隆的降解。     

除草剂阿特拉津的环境毒理研究进展

叙述了阿特拉津的应用概况及其在生产实践中所存在问题；阿特拉津在生物体内和环境中的降解代谢过程。综述了近年来国内外在阿特拉津的残留分析方法、环境毒理学和微生物降解等方面的研究进展。     

兽药在畜禽排泄物中的残留与降解研究进展

药物在环境中的暴露及其生态风险已成为国际上研究的热点,养殖业中大量使用的兽药已成为环境中药物的重要来源之一,动物体使用的兽药绝大部分首先以原药或代谢物的形式在动物排泄物中出现。本文综述了兽药在畜禽排泄物中的残留、降解及其影响因素,并介绍了残留兽药对畜禽排泄物堆肥过程的影响。     

Hydrolysis of sulfonylurea herbicides in soils and aqueous solutions: a review

Sulfonylureas are a unique group of herbicides used for controlling a range of weeds and some grasses in a variety of crops and vegetables. They have been extremely popular worldwide because of their low mammalian toxicity, low use rate, and unprecedented herbicidal activity. Knowledge about the fate and behavior of sulfonylurea herbicides in the soil-water environment appears to be of utmost importance for agronomic systems and environmental protection. Because these herbicides are applied at a very low rate, and their mobility is greatly affected by the chemicals' anionic nature in alkaline soils, a thorough understanding of their degradation/hydrolysis processes and mechanisms under aqueous and soil systems is important. This review brings together published information on the hydrolysis of several sulfonylureas in aqueous and soil solutions that includes the effects of pH, temperature, functional relationship between pH vs hydrolysis rate constants, and hydrolysis behavior of sulfonylureas in the presence of minerals. In addition, the transformations of sulfonylureas in soil, under laboratory and field experiments, have been discussed in connection with the compounds' varied structural features, i.e., sulfonylueas that are with or without the pyridinic, pyrimidine, and triazinic ring.     

水稻土中广灭灵残留动态及降解影响因子的研究

对水稻土中广灭灵残留消解动态及降解影响因子研究结果表明 ,广灭灵在 4种水稻土中降解符合 1级动力学方程C =C0 e-kt,其降解半衰期为 5 7～ 2 2 0d。广灭灵降解以微生物降解为主 ,土壤灭菌处理大大降低广灭灵降解速率 ,土壤理化性质、温度、湿度、pH值是影响广灭灵降解的重要因素。广灭灵降解速率与不同类型水稻土有机质含量呈显著负相关关系 ,相关系数为 - 0 8336。随温度上升而广灭灵降解有加速趋势 ,但常温 2 5℃时广灭灵降解速率高于 35℃处理 ,增加土壤湿度及施用石灰增加土壤 pH值均加快广灭灵降解速率     

Organic amendments from olive cake as a strategy to modify the degradation of sulfonylurea herbicides in soil

Amending soil with products rich in organic matter, such as raw olive cake or alperujo and its compost and vermicompost, could be a simple bioremediation strategy for soil pollutants such as pesticides. To investigate this hypothesis in relation to sulfonylurea herbicides, these amendments were applied to a Mediterranean agricultural soil at rates 4 times higher than agronomical dosage to stimulate biodegradation of chlorsulfuron, prosulfuron, and bensulfuron, added in a mixture to the soils. Degradation studies were conducted in microbially active and sterile soils to check the importance of biological and chemical degradation of sulfonylurea herbicides in nonamended and amended soil. The addition of alperujo stimulated soil microbial activity, as determined by dehydrogenase activity measurements, but it did not enhance the degradation of the sulfonylurea herbicides. In contrast, compost and vermicompost slightly favored the biological degradation of bensulfuron during the first week of incubation. Chlorsulfuron and prosulfuron were mainly degraded by chemical pathways in all substrates, which is probably due to a competitive or inhibitory phenomenon observed between chlorsulfuron and bensulfuron. The first-order kinetic equation satisfactorily explained the experimental data for chlorsulfuron and prosulfuron; however, a biphasic model, such as that proposed by Hoerl, better predicted the results obtained for bensulfuron.     

Transformation kinetics and mechanism of the sulfonylurea herbicides pyrazosulfuron ethyl and halosulfuron methyl in aqueous solutions

Pyrazosulfuron ethyl (PE) and halosulfuron methyl (HM) are two new highly active sulfonylurea herbicides that have been widely used for weed control in a variety of vegetables and other crops. These two herbicides have similar molecular structures, differing only in the substitutions on the pyrazole ring. Chemical hydrolysis is a primary process affecting the environmental fate of sulfonylurea pesticides. The hydrolytic transformation kinetics of PE and HM were investigated as a function of pH and temperature. For both herbicides, the hydrolysis rate was pH-dependent and increased with increasing temperature. The hydrolysis of both sulfonylureas was much faster in acidic or basic media than under neutral conditions. Identification of hydrolytic products by liquid chromatography-mass spectrometry (LC-MS) suggested that both PE and HM were subject to cleavage and contraction of the sulfonylurea bridge. The hydrolysis rate of HM was significantly higher than that of PE in alkaline solutions, despite their structural similarity. A chlorine substitution on HM's pyrazole ring makes HM more susceptible to bridge contraction than PE under basic conditions. The hydrolysis of HM and PE was relatively unaffected by the presence of cyclic oligosaccharides (cyclodextrins), indicating that natural OH-containing organic compounds occurring in aquatic environments may have little impact on the transformation of these sulfonylurea herbicides.     

竹炭固定化微生物对土壤中阿特拉津的降解研究

采用环境友好材料竹炭为主要载体,壳聚糖和海藻酸钠为辅助载体,固定从污泥中分离出的阿特拉津降解菌株,研究不同固定材料对降解菌生长的影响,以及固定化微生物对土壤中阿特拉津的降解效果.结果表明,竹炭对阿特拉津降解菌具有较强的吸附固定能力,且竹炭粒径越小,固定化效果越好.利用壳聚糖和海藻酸钠交联并加固阿特拉津降解菌,增大了固定化空间,显著增加了降解菌的生物量,并提高了阿特拉津的降解效率.1％壳聚糖+5％海藻酸钠+竹炭+降解菌颗粒对阿特拉津降解菌的固定化效果最佳,施用该微生物固定化颗粒28天后,砂姜黑土及红壤中阿特拉津残留率分别为48.07％和47.23％.     

Behavior of four sulfonylurea herbicides in the presence of hydroxy compounds

The behavior of four sulfonylurea herbicides (metsulfuron methyl, chlorsulfuron, chlorimuron ethyl, and bensulfuron methyl) was studied in the presence of various hydroxy compounds. When dissolved at 30 degrees C in simple primary, secondary, or tertiary alcohols (methanol, ethanol, isopropyl alcohol, and tert-butyl alcohol) and in glycerol or in poly(ethylene glycol), most of these herbicides underwent rapid alcoholysis involving the breakdown of the urea part of the molecule. The corresponding sulfonyl carbamate is recovered in high yields, along with a small amount of sulfonylamide formed in the concomitant hydrolysis. Degradation rate constants and the selectivity of conversion were established. The addition of buffered water (pH 7.0) inhibited the alcoholysis reaction, leaving only hydrolysis, as already observed with concentrated saccharide solutions. In phenol solution, slight herbicide hydrolysis was primarily observed. It appeared that alcoholysis reactions only occurred under very particular conditions when sulfonylurea herbicides are dissolved in pure alcohols, without buffered water. These results led to the conclusion that in soil, similar alcoholysis reactions seem unlikely.     

阿特拉津和乙草胺在玉米和土壤中残留动态研究

采用田间试验和气相色谱-质谱(GC-MS)联用的检测方法研究了阿特拉津和乙草胺在玉米和土壤中的消解动态及最终残留规律。结果表明,该方法阿特拉津最低检出浓度为0.08 ng g-1,添加浓度在10~250 ng g-1范围内,回收率在85%~97%之间,相对标准偏差(RSD)在10.0%~14.4%之间;乙草胺最低检出浓度为0.40 ng g-1,添加浓度在10~250 ng g-1范围内,回收率在102%~109%之间,相对标准偏差(RSD)在9.7%~14.0%之间。阿特拉津和乙草胺在土壤中的消解动态方程分别为C=1942.7e-0.0492T和C=916.53e-0.0343T,降解半衰期分别为14.1 d和20.2 d。38%阿特拉津水悬浮液、900 g L-1乙草胺乳油剂用于玉米田除草,施药剂量分别为5.25~10.50 g hm-2、2.25~4.50 g hm-2,在玉米播种后出苗前施药,施药1次,收获期玉米籽粒中阿特拉津残留量低于0.08 ng g-1、乙草胺残留量低于0.40 ng g-1,土壤中阿特拉津残留量低于3.3 ng g-1、乙草胺残留量低于12.4 ng g-1,均满足相应的限量标准。     

Degradation of diphenyl ether herbicides in soils

The gas chromatographic determination of CNP (2,4,6-trichlorophenyl 4-nitrophenyl ether), nitrofen (2,4-dichlorophenyl 4′-nitrophenyI ether), chlomethoxynil (2,4-dieblorophenyl 3′-methoxy-4′-nitrophenyl ether), CFNP (2,4-dichloro-6-fluorophenyl 4-nitrophenyl ether) and their amino derivatives in soils were carried out. Good recoveries from soils were obtained for the diphenyl ethers. On the other hand, satisfactory recoveries from soils were also obtained for the amino derivatives at high concentrations, but the recoveries at lower concentrations averaged about 66% for the least recovered compound.

The degradation of several diphenyl ether herbicides in two paddy soils were compared under flooded and upland conditions. The degradation was much slower under upland than under flooded conditions. Considerable amounts of their amino derivatives were produced in soils under flooded conditions, but not under upland conditions. It was suggested that the diphenyl ethers to the amino derivatives involved both chemical and microbial processes. CNP and chlomethoxynil degraded faster at lower concentrations than at higher ones.     

Effect of selected herbicides on yielding and malting quality of spring barley cultivars

The aim of the study was to determine the effect of herbicides on yields, yield components and malting quality of the grains of barley cultivars. Literature worldwide lacks works on the impact of herbicides on the brewing quality of barley. This work presents the results of field experiments and laboratory studies concerning the evaluation of the impact of herbicides, differing in terms of an active substance, on the yields, weed control and malting quality of selected cultivars of barley. The research was conducted in Poland. The herbicides affected the increase in grain yields of barley, due to their high effectiveness of weed control, resulting in an increase in the number of ears per area unit. Certain herbicides increased grain protein content and grain filling. As for malt extractivity, Kolbach index, Q index, diastatic power and beta-glucans content in wort, there were interactions between herbicides and cultivars. The impact of herbicides on parameters varied depending on cultivars. The herbicides, especially Chwastox Turbo 340 SL (MCPA?+?dicamba) and Secator 125 OD (amidosulfuron?+?iodosulfuron-methyl-sodium), worsened several (not many) malt quality parameters, depending on cultivars, but it did not contribute to disqualifying malting quality of grains. Therefore, all tested herbicides can be recommended for use by farmers.